CN101497668A - Homogeneous phase modifying method for cellulose in ion liquid - Google Patents
Homogeneous phase modifying method for cellulose in ion liquid Download PDFInfo
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- CN101497668A CN101497668A CNA2009100373684A CN200910037368A CN101497668A CN 101497668 A CN101497668 A CN 101497668A CN A2009100373684 A CNA2009100373684 A CN A2009100373684A CN 200910037368 A CN200910037368 A CN 200910037368A CN 101497668 A CN101497668 A CN 101497668A
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Abstract
The invention discloses a method of cellulose homogeneous-phase modification in ionic liquid. The method comprises the following steps: firstly, the cellulose is dried to obtain dry cellulose; then the dry cellulose is added in the ionic liquid and is dissolved to obtain the ionic liquid solution of the cellulose under the conditions of moisture isolation and stirring; the dimethyl sulfoxide is added in the cellulose solution to reduce the solution viscosity, and the solid modification reagent dissolved in the dimethyl sulfoxide in advance is added in the cellulose solution for cellulose modification; and finally the modified cellulose ionic liquid solution is added with organic solvent or water for cellulose regeneration, the sediment is leached, and the sediment is cleaned and dried to obtain cellulose derivative. The adopted cellulose homogeneous-phase modification method is simple and convenient in operation, short in time and good in effect. The invention is suitable for cellulose homogeneous-phase modification of the solid modification reagent in the ionic liquid.
Description
Technical field
The invention belongs to the Mierocrystalline cellulose field, the method for homogeneous phase modified-cellulose in particularly a kind of ionic liquid.
Background technology
As the abundantest renewable resources of occurring in nature, the total amount of Mierocrystalline cellulose in vegitabilia reaches 2.6 * 10 approximately
12T, the whole world has 1.0 * 10 approximately by the newly-generated Mierocrystalline cellulose of photosynthesis every year in addition
11T.At present, cellulose materials is used widely at numerous industrial circles such as fiber, papermaking, film, polymkeric substance, coating, but its application potential also is not developed fully.In recent years, along with the minimizing day by day of non-renewable fossil resource total amount such as oil, coal, the importance of Mierocrystalline cellulose renewable resources is remarkable day by day.Particularly since the eighties, along with people's environmental pollution problem growing interest and attention, many countries particularly developed country have classified the trans-utilization of renewable resourcess such as Mierocrystalline cellulose as the great strategy of economy and social development.
Mierocrystalline cellulose will become one of following most important industrial raw material, and preparation material of regenerated cellulose and derivatived cellulose are one of its most important trans-utilization modes.Yet, the cellulosic structure complexity, on chemical structure, Mierocrystalline cellulose is by β-1 by D-glucopyranose base, the linear high polymer that 4 glycosidic links are connected with each other all contains 3 free alcohol hydroxyls on each glucose unit in its molecule, this structure makes between cellulosic molecule and intramolecularly has extremely strong hydrogen bond action, strengthen the integrity and the rigidity of cellulose molecular chain, formed the crystallizing field and the less orderly pars amorpha of high-sequential in Mierocrystalline cellulose inside.Mierocrystalline cellulose inside exists a large amount of crystalline texture and intermolecular and intramolecular hydrogen bond, causes solvent and reaction reagent very low to cellulosic accessibility, and this has become the main bottleneck of restriction cellulose resource utilization.Since affirmation cellulosic molecule structure, numerous researchists are devoted to seek and develop suitable cellosolve system always, and particularly in recent years, this aspect has obtained bigger progress.It is reported N,N-dimethylacetamide/lithium chloride (DMAc/LiCl), N, dinethylformamide/four oxygen phenodiazine (DMF/N
2O
4), N-methyl-N-oxygen morpholine (NMNO), NaOH/ urea, methyl-sulphoxide/tetrabutyl ammonium fluoride (DMSO/TBAF) and fused salt hydrate be (as LiClO
43H
2O, LiSCN2H
2O etc.) equal effective dissolving cellulos.Yet, these solvents exist more or less instability, poisonous, shortcoming be difficult for to reclaim and costs an arm and a leg etc.
Ionic liquid claims watery fusion salt again, is in a liquid state under room temperature or nearly room temperature condition, is made up of organic cation and inorganic or organic anion usually.As a kind of emerging green solvent, ionic liquid is with its distinctive good dissolubility, strong polarity, non-volatile, not oxidation, be applied at numerous areas such as electrochemistry, extracting and separating, chemosynthesis, material preparations rapidly to premium propertiess such as water and air are stable, its huge application potential is reached common understanding in whole scientific circles, be considered to one of the most potential green solvent, its applied research becomes the focus of recent research at numerous areas.Existing research shows, ionic liquid not only can dissolving cellulos, but also the green reaction medium can be provided for the preparation of derivatived cellulose.By modification, can the processability fiber with excellent plain derivative, these derivatived celluloses can be used as tencel cellulose fiber and cellulose materials, have broad application prospects at industrial circles such as wastewater treatment, chemicals.Yet; cellulosic homogeneous phase modification mainly concentrates on the derivatize such as acetylize that carries out with liquid modifying reagent in the ionic liquid at present; and when adopting solid reaction reagent,, be difficult to realize the cellulose homogeneous-phase modification in modified system because solid reagent dissolves and needs the regular hour.Carboxymethyl cellulose, Mierocrystalline cellulose succinate monoester etc. are that the derivatived cellulose of properties-correcting agent preparation not only has important use in industry such as chemical, material, wastewater treatments with the solid reagent, and, can be used as further prepared in reaction type material of intermediate and medicine owing in cellulose macromolecule, introduced active stronger carboxyl function base.
Therefore, inquire into cellulose homogeneous-phase method of modifying in a kind of ionic liquid and have very important theory and practice meaning, have positive pushing effect for the preparation of Mierocrystalline cellulose infant industry material and new derivatives for the trans-utilization of Mierocrystalline cellulose renewable resources.
Summary of the invention
The objective of the invention is at the deficiencies in the prior art, the method for homogeneous phase modified-cellulose in a kind of ionic liquid is provided, this method can adopt the solid modifying agent to realize the cellulose homogeneous-phase modification in ionic liquid.
The object of the invention is achieved through the following technical solutions: the method for homogeneous phase modified-cellulose in a kind of ionic liquid specifically may further comprise the steps:
(1) be the bone dry fiber element with the Mierocrystalline cellulose drying;
(2) be solvent with ionic liquid 1-butyl-3-methyl imidazolitm chloride, plain at 80～130 ℃, bone dry fiber is to add in the ionic liquid bone dry fiber is plain under the condition of 0.2～3:100 with ion liquid mass ratio, dissolve 1～15h and obtain cellulosic ionic liquid solution under the condition of isolated moisture, dissolution process keeps evenly stirring;
(3) be 1～5:10ml/g according to methyl-sulphoxide with ion liquid volume mass ratio, in cellulosic ionic liquid solution, add methyl-sulphoxide to reduce soltion viscosity, be mixed into cellulose solution, dissolved solids modifying agent in advance in the methyl-sulphoxide of a equal volume again, it is joined in the cellulose solution, solid modifying agent and the unitary mol ratio of Mierocrystalline cellulose dextrose anhydrous are 2～8:1, under the condition of isolated moisture, Mierocrystalline cellulose is carried out modification, keep in the modifying process evenly stirring, modification temperature is controlled at 80～130 ℃, modification time 0.5～4h;
(4) after modification is finished, adding organic solvent or water make cellulose regenerated in reaction system, the organic solvent that is added or the volume of water are 1～5 times of the cellulosic ionic liquid solution volume that obtains of step (2), filter taking precipitate then, after using above-mentioned organic solvent or water with throw out washing 3～5 times, be drying to obtain derivatived cellulose.
Mierocrystalline cellulose described in the step (1) is for separating the Mierocrystalline cellulose obtain such as Eucalyptus Mierocrystalline cellulose or separating the Mierocrystalline cellulose that obtains such as straw cellulose, wheatgrass cellulose, bagasse cellulose etc. from agricultural crop straw from timber.
The solid acylating reagent is Succinic anhydried, Tetra hydro Phthalic anhydride or Monochloro Acetic Acid described in the step (3).
Organic solvent is ethanol, acetone or Virahol described in the step (4).
Drying described in step (1) and (4) preferably kept the air cycle drying 10～16 hours in 50～60 ℃ of baking ovens.
Cellulose regenerated among the present invention is to add excessive organic solvent or water to cellulose solution the dissolved Mierocrystalline cellulose is precipitated out once more.
The present invention compared with prior art has following outstanding advantage and beneficial effect:
1. the cellulose homogeneous-phase method of modifying of the present invention's employing is based on modification bone dry fiber element in the ionic liquid under given conditions, and the derivatived cellulose after the modification regenerates in specified conditions, and the product that obtains after washing, drying is derivatived cellulose;
2. the cellulose homogeneous-phase method of modifying of the present invention's employing can be used for the cellulose modified of solid modifying agent, and is easy and simple to handle, and modification time is short, the derivatived cellulose that can obtain having different degree of substitution;
3. the present invention is raw material with the Mierocrystalline cellulose, provides technical support to the development and use of Mierocrystalline cellulose renewable resources.
Embodiment
The present invention is described in further detail below in conjunction with embodiment, but the working of an invention mode is not limited thereto.
Embodiment 1
(1) bagasse cellulose is placed 50 ℃ of baking ovens keep the dry 16h of air cycle, obtain the bone dry fiber element;
(2) with ionic liquid 1-butyl-3-methyl imidazolitm chloride ([C
4Mim] Cl) be solvent, 80 ℃, over dry bagasse cellulose and [C
4Mim] mass ratio of Cl is under the condition of 0.2:100 bagasse cellulose to be added [C
4Mim] among the Cl, dissolving 1h obtains the ionic liquid solution of bagasse cellulose under isolated moisture and stirring condition.
(3) in the ionic liquid solution of bagasse cellulose, add methyl-sulphoxide according to the ion liquid ratio of 1mL methyl-sulphoxide/10g, to reduce soltion viscosity, be mixed into cellulose solution, in the methyl-sulphoxide of a equal volume, dissolve Succinic anhydried (Succinic anhydried and the unitary mol ratio of Mierocrystalline cellulose dextrose anhydrous are 4:1) more in advance, it is joined in the cellulose solution, under the condition of isolated moisture, Mierocrystalline cellulose is carried out modification, keep in the modifying process evenly stirring, modification temperature is controlled at 80 ℃, modification time 1h;
(4) adding 2 times of volumes (with respect to the ionic liquid solution volume of bagasse cellulose) Virahol in reaction system makes cellulose regenerated; the leaching throw out; with Virahol with throw out washing 3 times colourless after; place 50 ℃ of baking ovens to keep the dry 16h of air cycle, obtain succinylated bagasse cellulose derivative.
By the substitution value of titration measuring derivatived cellulose, prepared Mierocrystalline cellulose substitution value is 0.28.
Embodiment 2
(1) the Eucalyptus Mierocrystalline cellulose is placed 60 ℃ of baking ovens keep the dry 12h of air cycle, obtain the bone dry fiber element;
(2) be solvent with ionic liquid 1-butyl-3-methyl imidazolitm chloride ([C4mim] Cl), at 100 ℃, over dry Eucalyptus Mierocrystalline cellulose and [C
4Mim] mass ratio of Cl is under the condition of 1.5:100 the Eucalyptus Mierocrystalline cellulose to be added [C
4Mim] among the Cl, dissolving 8h obtains the cellulosic ionic liquid solution of Eucalyptus under isolated moisture and stirring condition.
(3) in the cellulosic ionic liquid solution of Eucalyptus, add methyl-sulphoxide according to the ion liquid ratio of 3mL methyl-sulphoxide/10g, to reduce soltion viscosity, be mixed into cellulose solution, in the methyl-sulphoxide of a equal volume, dissolve Succinic anhydried (Succinic anhydried and the unitary mol ratio of Mierocrystalline cellulose dextrose anhydrous are 2:1) more in advance, it is joined in the cellulose solution, under the condition of isolated moisture, Mierocrystalline cellulose is carried out modification, keep in the modifying process evenly stirring, modification temperature is controlled at 100 ℃, modification time 0.5h;
(4) adding 3 times of volumes (with respect to the cellulosic ionic liquid solution volume of Eucalyptus) ethanol in reaction system makes cellulose regenerated; the leaching throw out; with ethanol with throw out washing 5 times colourless after; place 60 ℃ of baking ovens to keep the dry 12h of air cycle, obtain succinylated Eucalyptus derivatived cellulose.
By the substitution value of titration measuring derivatived cellulose, prepared Mierocrystalline cellulose substitution value is 0.35.
Embodiment 3
(1) wheatgrass cellulose is placed 55 ℃ of baking ovens keep the dry 14h of air cycle, obtain the over dry wheatgrass cellulose;
(2) with ionic liquid 1-butyl-3-methyl imidazolitm chloride ([C
4Mim] Cl) be solvent, at 90 ℃, over dry wheatgrass cellulose and [C
4Mim] mass ratio of Cl is under the condition of 2.5:100 wheatgrass cellulose to be added [C
4Mim] among the Cl, dissolving 10h obtains the ionic liquid solution of wheatgrass cellulose under isolated moisture and stirring condition.
(3) in the ionic liquid solution of wheatgrass cellulose according to the ion liquid ratio of 2mL methyl-sulphoxide/10g, add methyl-sulphoxide, to reduce soltion viscosity, be mixed into cellulose solution, in the methyl-sulphoxide of a equal volume, dissolve Tetra hydro Phthalic anhydride (Tetra hydro Phthalic anhydride and the unitary mol ratio of Mierocrystalline cellulose dextrose anhydrous are 8:1) more in advance, it is joined in the cellulose solution, under the condition of isolated moisture, Mierocrystalline cellulose is carried out modification, keep in the modifying process evenly stirring, modification temperature is controlled at 90 ℃, modification time 2h;
(4) adding 4 times of volumes (with respect to the ionic liquid solution volume of wheatgrass cellulose) acetone in reaction system makes cellulose regenerated; the leaching throw out; with acetone 5 colourless being placed on of throw out washing are kept the dry 14h of air cycle in 55 ℃ of baking ovens, obtain the wheatgrass cellulose derivative of phthaloyl.
By the substitution value of titration measuring derivatived cellulose, prepared Mierocrystalline cellulose substitution value is 2.33.
Embodiment 4
(1) straw cellulose is placed 60 ℃ of baking ovens keep the dry 10h of air cycle, obtain the over dry straw cellulose;
(2) with ionic liquid 1-butyl-3-methyl imidazolitm chloride ([C
4Mim] Cl) be solvent, at 130 ℃, over dry straw cellulose and [C
4Mim] mass ratio of Cl is under the condition of 3.0:100 straw cellulose to be added [C
4Mim] among the Cl, dissolving 15h obtains the ionic liquid solution of straw cellulose under isolated moisture and stirring condition.
(3) in the ionic liquid solution of straw cellulose according to the ion liquid ratio of 5mL methyl-sulphoxide/10g, add methyl-sulphoxide, to reduce soltion viscosity, be mixed into cellulose solution, in the methyl-sulphoxide of a equal volume, dissolve Monochloro Acetic Acid (Monochloro Acetic Acid and the unitary mol ratio of Mierocrystalline cellulose dextrose anhydrous are 8:1) more in advance, it is joined in the cellulose solution, under the condition of isolated moisture, Mierocrystalline cellulose is carried out modification, keep in the modifying process evenly stirring, modification temperature is controlled at 130 ℃, modification time 4h;
(4) water of 5 times of volumes of adding (with respect to the ionic liquid solution volume of straw cellulose) makes cellulose regenerated in reaction system; the leaching throw out; water with throw out washing 4 times colourless after; place 60 ℃ of baking ovens to keep the dry 10h of air cycle, obtain the straw cellulose derivative of phthaloyl.
By the substitution value of titration measuring derivatived cellulose, prepared Mierocrystalline cellulose substitution value is 0.42.
The foregoing description is a preferred implementation of the present invention; but embodiments of the present invention are not restricted to the described embodiments; other any do not deviate from change, the modification done under spirit of the present invention and the principle, substitutes, combination, simplify; all should be the substitute mode of equivalence, be included within protection scope of the present invention.
Claims (6)
1, the method for homogeneous phase modified-cellulose in a kind of ionic liquid is characterized in that specifically comprising the steps:
(1) be the bone dry fiber element with the Mierocrystalline cellulose drying;
(2) be solvent with ionic liquid 1-butyl-3-methyl imidazolitm chloride, under 80～130 ℃, the bone dry fiber element is added in the ionic liquid, wherein the bone dry fiber element is 0.2～3:100 with ion liquid mass ratio, dissolve 1～15h and obtain cellulosic ionic liquid solution under the condition of isolated moisture, dissolution process keeps evenly stirring;
(3) be 1～5:10ml/g according to methyl-sulphoxide with ion liquid volume mass ratio, in cellulosic ionic liquid solution, add methyl-sulphoxide to reduce soltion viscosity, be mixed into cellulose solution, dissolved solids modifying agent in advance in the methyl-sulphoxide of a equal volume again, it is joined in the cellulose solution, solid modifying agent and the unitary mol ratio of Mierocrystalline cellulose dextrose anhydrous are 2～8:1, under the condition of isolated moisture, Mierocrystalline cellulose is carried out modification, keep in the modifying process evenly stirring, modification temperature is controlled at 80～130 ℃, modification time 0.5～4h;
(4) after modification is finished, adding organic solvent or water make cellulose regenerated in reaction system, the organic solvent that is added or the volume of water are 1～5 times of the cellulosic ionic liquid solution volume that obtains of step (2), filter taking precipitate then, throw out is washed after drying promptly obtain derivatived cellulose.
2, method according to claim 1 is characterized in that: Mierocrystalline cellulose described in the step (1) is for separating the Mierocrystalline cellulose that obtains from timber or agricultural crop straw.
3, method according to claim 1 is characterized in that: the solid modifying agent described in the step (3) is Succinic anhydried, Tetra hydro Phthalic anhydride or Monochloro Acetic Acid.
4, method according to claim 1 is characterized in that: the organic solvent described in the step (4) is ethanol, acetone or Virahol.
5, method according to claim 1 is characterized in that: the drying described in step (1) and (4) is for keeping air cycle drying 10～16h in 50～60 ℃ of baking ovens.
6, method according to claim 1 is characterized in that: the washing described in the step (4) is for an organic solvent or water washing 3～5 times.
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| CN102504274A (en) * | 2011-09-29 | 2012-06-20 | 中国科学院过程工程研究所 | Method for homogeneously derivatizing plant fiber raw material by taking ionic liquid as medium |
| CN102791911A (en) * | 2010-03-05 | 2012-11-21 | 奥林巴斯株式会社 | Cellulose nanofibers, method for producing same, composite resin composition and molded body |
| CN102863543A (en) * | 2012-09-10 | 2013-01-09 | 华南理工大学 | Water-soluble cationic cellulose material and preparation method thereof |
| CN105175342A (en) * | 2015-10-14 | 2015-12-23 | 大连工业大学 | Ionic liquid and method for homogeneous phase-modified reed-reinforced PE (polyethylene) composite material thereof |
| CN105461815A (en) * | 2016-01-13 | 2016-04-06 | 江苏科技大学 | Method for grafting anhydride onto cellulosic material in ionic liquid to prepare carboxyl cellulose |
| CN106661834A (en) * | 2014-07-10 | 2017-05-10 | 利芙科学私人有限公司 | Methods for treating lignocellulosic material |
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| CN102791911A (en) * | 2010-03-05 | 2012-11-21 | 奥林巴斯株式会社 | Cellulose nanofibers, method for producing same, composite resin composition and molded body |
| CN102504274A (en) * | 2011-09-29 | 2012-06-20 | 中国科学院过程工程研究所 | Method for homogeneously derivatizing plant fiber raw material by taking ionic liquid as medium |
| CN102504274B (en) * | 2011-09-29 | 2014-06-04 | 中国科学院过程工程研究所 | Method for homogeneously derivatizing plant fiber raw material by taking ionic liquid as medium |
| CN102863543A (en) * | 2012-09-10 | 2013-01-09 | 华南理工大学 | Water-soluble cationic cellulose material and preparation method thereof |
| CN102863543B (en) * | 2012-09-10 | 2015-03-11 | 华南理工大学 | Water-soluble cationic cellulose material and preparation method thereof |
| US11332768B2 (en) | 2014-07-10 | 2022-05-17 | Leaf Sciences Pty Ltd | Methods for hydrolysing lignocellulosic material |
| CN106661834B (en) * | 2014-07-10 | 2020-09-15 | 利芙科学私人有限公司 | Method for treating lignocellulosic material |
| CN106661834A (en) * | 2014-07-10 | 2017-05-10 | 利芙科学私人有限公司 | Methods for treating lignocellulosic material |
| CN105175342B (en) * | 2015-10-14 | 2018-07-20 | 大连工业大学 | A kind of method of ionic liquid and its homogeneous modified reed enhancing PE composite materials |
| CN105175342A (en) * | 2015-10-14 | 2015-12-23 | 大连工业大学 | Ionic liquid and method for homogeneous phase-modified reed-reinforced PE (polyethylene) composite material thereof |
| CN105461815A (en) * | 2016-01-13 | 2016-04-06 | 江苏科技大学 | Method for grafting anhydride onto cellulosic material in ionic liquid to prepare carboxyl cellulose |
| CN106955359A (en) * | 2017-03-29 | 2017-07-18 | 齐鲁工业大学 | A kind of slow releasing carrier of medication and preparation method based on butanedioic anhydride modification cellulose |
| CN106955359B (en) * | 2017-03-29 | 2019-12-20 | 齐鲁工业大学 | Drug sustained-release carrier based on succinic anhydride modified cellulose and preparation method thereof |
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